A method for preparing information storage material based on photochromic effect

Abstract

The invention discloses a method for preparing an information storage material based on a photochromic effect, belonging to the technical field of inorganic photochromic functional luminescent materials. The information storage material based on a photochromic effect of the invention has the chemical formula: A2Ge4O9:xBi 3+ ; Wherein, A includes one or more of Li, Na, K and Rb; x is Bi 3+ The doping amount is 0≤x≤0.08. The surface color of the information storage material of the present invention changes from white to yellow under ultraviolet light, and the color can be reversibly changed, so that information can be written, stored and erased based on the photochromic effect.

Description

Technical Field

[0001] The invention relates to the technical field of inorganic photochromic functional luminescent materials, and in particular to a method for preparing an information storage material based on the photochromic effect. Background Art

[0002] Long afterglow materials were once considered to be good optical information storage materials. However, the trap half-width in some long afterglow materials is large, so the afterglow will interfere with the reading of information.

[0003] When a photochromic material is exposed to electromagnetic waves of a certain wavelength and intensity, its surface color changes from one color to another, and the two states have clearly distinguishable absorption spectra or diffuse reflectance spectra. After exposure to electromagnetic waves of another wavelength or heat treatment, it returns to its original color (photochromic materials can "write" optical information under the irradiation of light of a certain wavelength; and can "read" optical information under the irradiation of light of another wavelength or heat treatment). Although photochromic materials have developed rapidly in the past two or three decades, especially organic photochromic materials have achieved outstanding results in commercial applications, the inherent defects of organic photochromic materials limit its further development in application, such as the organic matter used in preparation is toxic and polluting to the environment, poor fatigue resistance, poor thermal stability, and easy oxidation, resulting in reduced or even loss of color change performance. In contrast, inorganic photochromic materials have the advantages of better fatigue resistance, stronger thermal stability, faster color change reaction rate and longer color change duration, but the research on the storage duration of information storage and the number of achievable readings needs to be deepened. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing an information storage material based on the photochromic effect to solve the problems existing in the above-mentioned prior art. The information storage material of the present invention changes its surface color from white to yellow under ultraviolet light, and can change reversibly, so that information can be written, stored and erased based on the photochromic effect.

[0005] To achieve the above object, the present invention provides the following solutions:

[0006] One of the technical solutions of the present invention: an information storage material based on photochromic effect, the chemical formula is: A 2 Ge 4 O 9 :xBi 3+ ;

[0007] wherein A includes one or more of Li, Na, K and Rb;

[0008] x is Bi 3+ Doping amount (molar amount), 0≤x≤0.08.

[0009] Bi 3+ It can produce photochromic effect, and Bi 3+ It can play a role in regulating the photochromic effect.

[0010] The second technical solution of the present invention is a method for preparing the above-mentioned information storage material, the preparation method comprising the following steps:

[0011] According to the stoichiometric ratio in the chemical formula, the A-containing compound, the Ge-containing compound and the Bi-containing compound are weighed respectively, mixed and ground evenly, and calcined in an air atmosphere to obtain the information storage material.

[0012] Furthermore, the A-containing compound is an A-containing carbonate.

[0013] Furthermore, the A-containing carbonate is lithium carbonate, sodium carbonate, potassium carbonate and rubidium carbonate.

[0014] Furthermore, the Ge-containing compound includes germanium oxide.

[0015] Furthermore, the Bi-containing compound includes bismuth oxide.

[0016] Furthermore, the calcination temperature is 800-900° C. and the calcination time is 3-6 hours.

[0017] Furthermore, when A includes more than one of Li, Na, K and Rb, the same molar amount is used for each element.

[0018] The third technical solution of the present invention: an application of the above-mentioned information storage material in the preparation of optical switches, anti-counterfeiting materials, decorative materials, optical device materials, optical information storage sensors or radiation meters.

[0019] The present invention discloses the following technical effects:

[0020] (1) The information storage material (photochromic material) of the present invention changes its surface color from white to yellow under ultraviolet light, and can change reversibly, so that information can be written, stored and erased based on the photochromic effect.

[0021] (2) The information storage material of the present invention is a trivalent bismuth ion-doped germanate photochromic material, which can undergo a reversible color change under alternating irradiation of ultraviolet light and visible light.

[0022] (3) The information storage material (photochromic material) of the present invention is an inorganic photochromic material. Under ultraviolet light, the color of the sample surface changes from white to yellow. Under long-wavelength (365-450nm) light or heat treatment (about 300°C), the color of the sample surface returns to white, and it has the advantages of good fatigue resistance and thermal stability. The inorganic photochromic material of the present invention can be used in the fields of optical switches, anti-counterfeiting, decoration, optical device materials, optical information storage sensors, and radiation meters.

[0023] (4) The information storage material preparation method of the present invention is simple and the requirements for equipment are relatively simple; the materials used in the present invention are easily available and relatively low in price. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0025] Figure 1 The diffuse reflectance spectrum of the photochromic material prepared in Example 1 of the present invention before and after ultraviolet light irradiation;

[0026] Figure 2 The diffuse reflectance spectrum of the photochromic material prepared in Example 2 of the present invention before and after ultraviolet light irradiation;

[0027] Figure 3 The diffuse reflectance spectrum of the photochromic material prepared in Example 3 of the present invention before and after ultraviolet light irradiation;

[0028] Figure 4 The diffuse reflectance spectrum of the photochromic material prepared in Example 4 of the present invention before and after ultraviolet light irradiation;

[0029] Figure 5 The diffuse reflectance spectrum of the photochromic material prepared in Example 5 of the present invention before and after ultraviolet light irradiation;

[0030] Figure 6 The diffuse reflectance spectrum of the photochromic material prepared in Example 6 of the present invention before and after ultraviolet light irradiation;

[0031] Figure 7 The diffuse reflectance spectrum of the photochromic material prepared in Example 7 of the present invention before and after ultraviolet light irradiation;

[0032] Figure 8 The diffuse reflectance spectrum of the photochromic material prepared in Example 8 of the present invention before and after ultraviolet light irradiation;

[0033] Fig. 9 The diffuse reflectance spectrum of the photochromic material prepared in Example 9 of the present invention before and after ultraviolet light irradiation;

[0034] Fig.10 The diffuse reflectance spectrum of the photochromic material prepared in Example 10 of the present invention before and after ultraviolet light irradiation;

[0035] Fig.11 The diffuse reflectance spectrum of the photochromic material prepared in Example 11 of the present invention before and after ultraviolet light irradiation;

[0036] Fig.12 The diffuse reflectance spectrum of the photochromic material prepared in Example 12 of the present invention before and after ultraviolet light irradiation;

[0037] Fig.13 The diffuse reflectance spectrum of the photochromic material prepared in Example 13 of the present invention before and after ultraviolet light irradiation;

[0038] Fig.14 The diffuse reflectance spectrum of the photochromic material prepared in Example 14 of the present invention before and after ultraviolet light irradiation;

[0039] Fig.15 The diffuse reflectance spectrum of the photochromic material prepared in Example 15 of the present invention before and after ultraviolet light irradiation;

[0040] Fig.16 LiRbGe prepared in Example 1 of the present invention 4 O 9 :0.0025Bi 3+ XRD pattern of

[0041] Fig.17 KRbGe prepared in Example 2 of the present invention 4 O 9 :0.03Bi 3+ XRD pattern of

[0042] Fig.18 NaRbGe prepared in Example 8 of the present invention 4 O 9 :0.025Bi 3+ XRD pattern of

[0043] Fig.19 Rb prepared in Example 13 of the present invention 2 Ge 4 O 9 :0.01Bi 3+ XRD pattern of

[0044] Fig. 20 LiRbGe prepared in Example 1 of the present invention 4 O9 :0.0025Bi 3+ Relative intensity change diagram of cyclic use;

[0045] Fig.21 KRbGe prepared in Example 2 of the present invention 4 O 9 :0.03Bi 3+ Relative intensity change diagram of cyclic use;

[0046] Fig. 22 The NaRbGe prepared in Example 9 of the present invention 4 O 9 :0.05Bi 3+ Relative intensity variation graph of cyclic use. DETAILED DESCRIPTION

[0047] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0048] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0049] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0050] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present application description and examples are exemplary only.

[0051] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0052] The lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, germanium oxide and bismuth oxide used in the following examples of the present invention are all analytically pure, with a purity of 99.99%.

[0053] Example 1

[0054] According to the chemical formula LiRbGe 4 O 9 :0.0025Bi 3+ Weigh lithium carbonate, rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat to 800 ° C in an air atmosphere, keep warm for 5 hours, cool naturally to room temperature, and grind them into fine powder to obtain the photochromic material LiRbGe 4 O 9 :0.0025Bi 3+ .

[0055] Example 2

[0056] According to the chemical formula KRbGe 4 O 9 :0.03Bi 3+ Weigh potassium carbonate, rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat to 900 ° C in an air atmosphere, keep warm for 3 hours, cool naturally to room temperature, and grind them into fine powder to obtain the photochromic material KRbGe 4 O 9 :0.03Bi 3+ .

[0057] Example 3

[0058] According to the chemical formula KRbGe 4 O 9 :0.05Bi 3+ Weigh potassium carbonate, rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat to 900 ° C in an air atmosphere, keep warm for 3 hours, cool naturally to room temperature, and grind them into fine powder to obtain the photochromic material KRbGe 4 O 9 :0.05Bi 3+ .

[0059] Example 4

[0060] According to the chemical formula KRbGe 4 O 9 :0.07Bi 3+Weigh potassium carbonate, rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat to 900 ° C in an air atmosphere, keep warm for 3 hours, cool naturally to room temperature, and grind them into fine powder to obtain the photochromic material KRbGe 4 O 9 :0.07Bi 3+ .

[0061] Example 5

[0062] According to the chemical formula NaRbGe 4 O 9 :0.0025Bi 3+ Weigh sodium carbonate, rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat to 850 ° C in an air atmosphere, keep warm for 5 hours, cool naturally to room temperature, and grind them into fine powder to obtain the photochromic material NaRbGe 4 O 9 :0.0025Bi 3+ .

[0063] Example 6

[0064] According to the chemical formula NaRbGe 4 O 9 :0.005Bi 3+ Weigh sodium carbonate, rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat to 850 ° C in an air atmosphere, keep warm for 5 hours, cool naturally to room temperature, and grind them into fine powder to obtain the photochromic material NaRbGe 4 O 9 :0.005Bi 3+ .

[0065] Example 7

[0066] According to the chemical formula NaRbGe 4 O 9 :0.01Bi 3+ Weigh sodium carbonate, rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat to 850 ° C in an air atmosphere, keep warm for 5 hours, cool naturally to room temperature, and grind them into fine powder to obtain the photochromic material NaRbGe 4 O 9 :0.01Bi 3+ .

[0067] Example 8

[0068] According to the chemical formula NaRbGe 4 O 9 :0.025Bi3+ Weigh sodium carbonate, rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat them to 850°C in an air atmosphere and keep them warm for 5 hours. After cooling naturally to room temperature, grind them into fine powder to obtain the photochromic material NaRbGe 4 O 9 :0.025Bi 3+ .

[0069] Example 9

[0070] According to the chemical formula NaRbGe 4 O 9 :0.05Bi 3+ Weigh sodium carbonate, rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat to 850 ° C in an air atmosphere, keep warm for 5 hours, cool naturally to room temperature, and grind them into fine powder to obtain the photochromic material NaRbGe 4 O 9 :0.05Bi 3+ .

[0071] Example 10

[0072] According to the chemical formula NaRbGe 4 O 9 :0.08Bi 3+ Weigh sodium carbonate, rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat to 850 ° C in an air atmosphere, keep warm for 5 hours, cool naturally to room temperature, and grind them into fine powder to obtain the photochromic material NaRbGe 4 O 9 :0.08Bi 3+ .

[0073] Embodiment 11

[0074] According to the chemical formula Rb 2 Ge 4 O 9 Weigh rubidium carbonate and germanium oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat to 900℃ in an air atmosphere, keep warm for 6 hours, cool naturally to room temperature, and grind them into fine powder to obtain the photochromic material Rb 2 Ge 4 O 9 .

[0075] Example 12

[0076] According to the chemical formula Rb 2 Ge 4 O 9 :0.005Bi3+ Weigh rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat them to 900°C in an air atmosphere, keep them warm for 6 hours, cool them naturally to room temperature, and grind them into fine powder to obtain the photochromic material Rb 2 Ge 4 O 9 :0.005Bi 3+ .

[0077] Embodiment 13

[0078] According to the chemical formula Rb 2 Ge 4 O 9 :0.01Bi 3+ Weigh rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat them to 900°C in an air atmosphere, keep them warm for 6 hours, cool them naturally to room temperature, and grind them into fine powder to obtain the photochromic material Rb 2 Ge 4 O 9 :0.01Bi 3+ .

[0079] Embodiment 14

[0080] According to the chemical formula Rb 2 Ge 4 O 9 :0.02Bi 3+ Weigh rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat them to 900°C in an air atmosphere, keep them warm for 6 hours, cool them naturally to room temperature, and grind them into fine powder to obtain the photochromic material Rb 2 Ge 4 O 9 :0.02Bi 3+ .

[0081] Embodiment 15

[0082] According to the chemical formula Rb 2 Ge 4 O 9 :0.05Bi 3+ Weigh rubidium carbonate, germanium oxide, and bismuth oxide, mix and grind them evenly, put them into a corundum ark, and then place them in a muffle furnace. Heat them to 900°C in an air atmosphere, keep them warm for 6 hours, cool them naturally to room temperature, and grind them into fine powder to obtain the photochromic material Rb 2 Ge 4 O 9 :0.05Bi 3+ .

[0083] Effect Example 1

[0084] The diffuse reflectance spectrum of the photochromic material (sample) prepared in the embodiment of the present invention before and after ultraviolet light irradiation (after ultraviolet light irradiation: after ultraviolet light irradiation for 4 minutes) is measured. The results are shown in Figure 1 to Figure 15 .

[0085] Figure 1 The diffuse reflectance spectrum of the sample prepared in Example 1 of the present invention before and after ultraviolet light irradiation; Figure 2 The diffuse reflectance spectrum of the sample prepared in Example 2 of the present invention before and after ultraviolet light irradiation; Figure 3 The diffuse reflectance spectrum of the sample prepared in Example 3 of the present invention before and after ultraviolet light irradiation; Figure 4 The diffuse reflectance spectrum of the sample prepared in Example 4 of the present invention before and after ultraviolet light irradiation; Figure 5 The diffuse reflectance spectrum of the sample prepared in Example 5 of the present invention before and after ultraviolet light irradiation; Figure 6 The diffuse reflectance spectrum of the sample prepared in Example 6 of the present invention before and after ultraviolet light irradiation; Figure 7 The diffuse reflectance spectrum of the sample prepared in Example 7 of the present invention before and after ultraviolet light irradiation; Figure 8 The diffuse reflectance spectrum of the sample prepared in Example 8 of the present invention before and after ultraviolet light irradiation; Fig. 9 The diffuse reflectance spectrum of the sample prepared in Example 9 of the present invention before and after ultraviolet light irradiation; Fig.10 The diffuse reflectance spectrum of the sample prepared in Example 10 of the present invention before and after ultraviolet light irradiation; Fig.11 The diffuse reflectance spectrum of the sample prepared in Example 11 of the present invention before and after ultraviolet light irradiation; Fig.12 The diffuse reflectance spectrum of the sample prepared in Example 12 of the present invention before and after ultraviolet light irradiation; Fig.13 The diffuse reflectance spectrum of the sample prepared in Example 13 of the present invention before and after ultraviolet light irradiation; Fig.14 The diffuse reflectance spectrum of the sample prepared in Example 14 of the present invention before and after ultraviolet light irradiation; Fig.15 This is the diffuse reflectance spectrum of the sample prepared in Example 15 of the present invention before and after ultraviolet light irradiation.

[0086] Effect Example 2

[0087] LiRbGe prepared in Example 1 of the present invention 4 O 9 :0.0025Bi 3+ The XRD pattern of Fig.16 ; KRbGe prepared in Example 2 of the present invention 4 O 9 :0.03Bi 3+ The XRD pattern of Fig.17 ; NaRbGe prepared in Example 8 of the present invention 4 O 9:0.025Bi 3+ The XRD pattern of Fig.18 ; Rb prepared in Example 13 of the present invention 2 Ge 4 O 9 :0.01Bi 3+ The XRD pattern of Fig.19 .

[0088] Effect Example 3

[0089] LiRbGe prepared in Example 1 of the present invention 4 O 9 :0.0025Bi 3+ The relative intensity change diagram of cyclic use is shown in Fig. 20 ; KRbGe prepared in Example 2 of the present invention 4 O 9 :0.03Bi 3+ The relative intensity change diagram of cyclic use is shown in Fig.21 ; NaRbGe prepared in Example 9 of the present invention 4 O 9 :0.05Bi 3+ The relative intensity change diagram of cyclic use is shown in Fig. 22 .

[0090] from Figures 20-22 It can be seen that after multiple cycles of ultraviolet and visible light irradiation, the photochromic properties of the material are not significantly affected, indicating that the material has good reversibility and anti-fatigue properties.

[0091] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. An information storage material based on photochromic effect, characterized in that: The chemical formula is: A2Ge4O9:xBi 3+ ; wherein A includes one or more of Li, Na, K and Rb; x is Bi 3+ The doping molar amount, 0<x≤0.

08.

2. A method for preparing the information storage material according to claim 1, characterized in that: The preparation method comprises the following steps: According to the stoichiometric ratio in the chemical formula, the A-containing compound, the Ge-containing compound and the Bi-containing compound are weighed respectively, mixed and ground evenly, and calcined in an air atmosphere to obtain the information storage material.

3. The method for preparing the information storage material according to claim 2, characterized in that: The A-containing compound is an A-containing carbonate.

4. The method for preparing the information storage material according to claim 2, characterized in that: The Ge-containing compound includes germanium oxide.

5. The method for preparing the information storage material according to claim 2, characterized in that: The Bi-containing compound includes bismuth oxide.

6. The method for preparing the information storage material according to claim 2, characterized in that: The calcination temperature is 800-900° C. and the calcination time is 3-6 hours.

7. Use of the information storage material according to claim 1 in the preparation of optical switches, anti-counterfeiting materials, decorative materials, optical device materials, optical information storage sensors or radiation meters.

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